Adducts of long chain unsaturated compounds



United States Patent Ofiice Patented Oct. 28, 1958 ADDUCTS OF LONG CHAINUNSATURATED COMPOUNDS Curtis W. Smith, Berkeley, Calif., assignor toShell Development Company, New York, N. Y., a corporation of Delaware NDrawing. Application January 24, 1956 Serial No. 561,160

9 Claims. (Cl. 260--346.8)

ment of better curing agents for these versatile resins.

The requirements for improved curing agents have resulted in thedevelopment of many such curing agents and these curing agents havevaried widely depending on the particular resin used, its application insurface coatings, in castings, and the like.

It is an object of this invention to provide a novel class of curingagents for polyglycidyl ethers. It is another object of this inventionto provide low cost curing agents for such resins that are easy andsimple to manufacture. It is yet another object of this invention toprovide a novel class of curing agents that may be used for both coatingor casting resin compositions and thereby simplifying the curing processfor fabricators of polyglycidyl ether resin products. Still otherobjects of this invention will appear as the description proceeds.

It has now been found that these and other objects may be accomplishedby novel adducts which are produced by the reaction of maleic anhydridewith a compound having the formula wherein R is a divalent chain havingfrom 14 to 26 carbon atoms, said divalent chain having two unsaturatedlinkages which are at least four carbon atoms removed from the carbonylgroups, R is a functional group selected from alkyl, aryl, aralkyl, -OH,-NH and 0R R being alkyl, aryl or aralkyl.

It is seen then that the products of this invention are those that maybe obtained by the reaction of maleic anhyclride with dicarboxylicacids, ester, ketones or amides having at least 16 carbon atoms betweenthe -COR groups and having at least two ethylenic groups which arenon-conjugated and that are at least four carbon atoms removed from theterminal COR groups. R may be either branch or straight chain but in anycase it will contain a minimum of carbon atoms between the carbonylgroups.

The unsaturated diacids and diesters employed in the preparation ofthese novel products are described in copending application Serial No.432,026, filed May 24, 1954, and the diamides which may be used aredescribed in copending application Serial No. 486,033, filed February 3,1955. The diketones and the processes for preparing the same aredescribed in U. S. Patent 2,671,810.

Although the acids, esters and amides are fully described in the abovementioned copending applications, it is desirable to briefly outlinetheir nature.

Essentially, the amides may be prepared from their corresponding acids.The acids and esters may be 013* tained by treating (a) a cyclicperoxide of the formula /O O Y wherein A is a divalent radical having adivalent chain of 3 to 9 carbon atoms, X is a radical of the groupconsisting of hydrogen, hydroxyl and hydrocarbon radicals of not morethan 12 carbon atoms and Y is a hydrogen atom or a radical with (b) aconjugated diethyl compound of 4 to 18 carbon atoms and in the presenceof (c) a redox catawherein the symbol A is a divalent radical of thetype previously indicated. The peroxide thus obtained is mainly adihydroxy peroxide and the ultimate product is a diacid. If the reactionis conducted additionally in the presence of an alcohol such asmethanol, the ultimate product is mainly a diester although there willbe quantities of the diacid present. These peroxides can be produced asdescribed in Milas Patent U. S. 2,298,405, the products from equimolaramounts of cyclic ketone and hydrogen peroxide being, as pointed out byCriegee, Ann., vol. 565, page 7 (1949), and by Cooper and Davison, J.Chem. Soc, page 1180 (1952), chiefly the 1-hydroXy-1-hydroperoxydicycloalkanyl peroxides Preferred cyclic peroxides for usein the process are the 1,1-hydrodicycloalkanyl peroxides and thel-hydroxycyclcalkanyl hydroperoxides no OOH /OOH As conjugateddiethylenic compounds which can be reacted with the foregoing cycliccompounds are included conjugated diolefinssuch as 1,3-butadiene,1,3-pentadiene, isoprene, dimethyl 1,3 butadiene, 1,3,5 hexatriene, 2ethyl 1,3 pentadiene, 2,4 octadiene, 1,1 dimethyl- 3 tertiary butyl 1,3butadiene, chloroprene, 2,3 dichloro 1,3 butadiene, l chloro 2 methyland1,3- butadiene.

From the acids thus prepared the corresponding diamides may be preparedas described in copending application Serial No. 486,033, filed February3, 1955.

The acids may be either straight chain or branch chain or mixturesthereof. Among such acids are 8,12- eico s'adi'ene 1,20 dioic acid, 8,10dimethyl 8 vinyl- IO-Octade'cene-I,18-dioic acid, 8,11-dimethyl-8vinyl-10- octadecene-1,18-dioic acid, 10-methyl-8-isopropenyl-10-octadecene-1,18-dioic acid, 11-methyl-8-isopropenyl-l0-octadecene-1,18-dioic acid, 4,15-dimethyl-8-vinyl-10-octadecene-1,l8-dioic acid, 3,4-, 3,16-, 3,17-, 4,6-, 4,17- and4,18-dimethyl-8,lZ-eicbsadiene-LZO-dioic acid.

Among the esters that may be used are dimethyl-8-vinyl-10-octadecene-l8-dioate, dimethyl-8, l 2eicosadiene- 1,20-dioate,the 8,13- and the 9,12-dimethyl derivatives thereof, dimethyl7,1l-octadecadiene-l,18-dioate,dimethyl-7-vinyl-9-hexadecene-1,16-dioate. Also the dimethyl ester ofdichloro-7,l1-octadecene-1,l8-dioic acid, dimethyl 4,17 dimethyl 8,12eicosadiene 1,20- dioic acid, and4,1S-dimethyl-S-vinyl-10-octadecene-1,l8- dioic acid. Dimethyl esters oftetramethyl-8,1Z-eicosadione-1,20-dioic acids having the four methylgroups in the 3- or 4-, 8- or 9-, 12- or 13, and 17- or 18- positions,respectively, and the like.

Among the dia'mides are 8,12-eicosadiene-1,20-diamide, 8,12 diisopropyl8,12 eicosadiene 1,20- diamide,3,16'dichloro-8,12-eicosadiene-l,2-diamide, N- butyl-N-octyl8,12-eicosadiene-1,20-diamide, N,N-diallyl 8,16 dichloro 8,12eicosadiene 1,20 diamide, octadecadiene 1,18 diamide, N,N' diisopropyl4,15- dimethyl 8 vinyl 10 octadecene 1,18 diamide, N,N diallyl 10,14tetracosadiene 1,24 diamide, N,N-(4-arninobutyl) 8,12 eicosadiene 1,20diamide, N,N di( aminohexyl) 8,12 eicosadiene 1,20- diamide, N,N' di(8aminooctyl) 3,3,4,4 tetramethyl- 8,12 eicosadiene 1,18 diamide, N,N,N'N'tetraethyl 8,12 eicosadiene 1,20 diamide, N,N' di(2 ethylphenyl)8,12-eicosadiene-1,20-diamide, N,N'-di(furfuryl) 7,11 octadecadiene 1,18diamide, N,N' di(4- arninophenyl) 7,1l-octadecadiene-1,18-diamide, N,N-di(4 aminonaphthyl) 7,11 octadecadiene 1,18 diamide N,N'-dioctadecyl and8,12-eicosadiene-1,20-diamide.

Among the diketones that may be used are 9,13-docosadienc-2,21-dione,9,l3-docosadiene-2,21-dione, 1,22- diphenyl-9,13-docosadiene-2,2l-dione,and the like.

The diacids, diesters and diamides may be used in mixtures and undercertain circumstances it is preferred as an economy step. Thus forexample, in the above mentioned copending application Serial No.432,026, the processes there described often produce mixtures of acidsand esters which are further mixtures of branched and straight chainproducts, and rather than separate them, they may be used in admixturewithout adverse eifect.

While the configuration of the adducts of this invention are not knownfor certain and will vary widely depending on the starting materials, atypical linear monoadduct is produced, for example, as follows:

and A is a divalent radical having a chain of 4 to 9 carbon atoms. Itshould be understood that the claims are not limited by any theoreticalconsiderations or any particular structural formula. The followingexamples will illustrate rather than limit the embodiments of thisinvention as recited in the claims. All proportions are in parts byweight unless otherwise indicated.

EXAMPLE I p 183 parts (05 mole) of dimethyl ester of 8,12-eicosene-1,20-dioate, having the formula and 59 parts (0.60 mole) of maleicanhydride are heated at 200 C. for about 7 hours while maintaining thereaction mass under an atmosphere of carbon dioxide. The reactionmixture is then dissolved in 450 parts of chloroform and then washedthree times with 10% aqueous M1 50 4 parts of unreacted maleic anhydrideis recovered indicating that each mole of the ester fixes 1.2 moles ofmaleic anhydride. The chloroform solution is dried over anhydrous sodiumsulfate, filtered and then stripped. The product, 290 parts, is aviscous, clear, light amber liquid having the following analysis:

Found Calculated for Anhydride Value, moles/ g 0. 13 .22 Total acidity,electromctric eq./100 g .332 43 Total Sap. N 0., eq./l00 g., Notcorrected for acidity .88 .80 Iodine No., g./10O g. Woburn 79 109 Theproduct has the probable configuration of Formula I above where R is OCHand the As are -C H EXAMPLE II The procedure of E. ample l is repeatedexcept that 16.7

118 parts (1.2 moles) of maleic anhydride is used. parts of unreactedanhydride is removed indicating that one mole of the ester binds 2.1moles of the anhydride.

The yield is 282 parts of the corresponding diadduct of Formula it aboveand has the following analysis:

Found Calculated for CaoHnOro Anhydrlde Value, moles/100 g 1. .057 .355Total Acidity eq./10O g 60 .71 Total Sap. No., eq./100 g., Not correctedfor acidity t 1. 0 1.07 Iodine N 0., g./100 g. Wobutn 57.0 90. 2

EXAMPLE III The procedure of Example I is followed except that 216 parts(2.2 moles) of maleic anhydride is initially charged into the reactor.77 parts of unreacted maleic anhydride is recovered indicating. that thecorresponding triadduct of Formula III is formed. The yield is 325 partsof a clear brown viscous liquid having the following analysis:

Found Calculated for Anhydride Value, moles/100 g .45 Total Acidityeq./10O g 70 .91 Total Sap. N0., eq./10O g., Not corrected foracidity 1. 3 1. 2 Iodine No., g./100 g. Woburn 39.0 76. 8

EXAMPLE IV EXAMPLE V As in the above examples, 170 parts of thecorresponding amide is reacted with 59 parts, 118 parts and 216 parts,respectively, of maleic anhydride. The mono, diand tri-adduct of8,12-eicosene-1,20-diamide is produced.

EXAMPLE VI As in the above examples, 167 parts of9,13-docosadiene-2,2l-dione is reacted with 59, H8 and 216 parts ofmaleic anhydride to form the mono-, di-, and triadducts, respectively,of the corresponding diketone.

EXAMPLE VII The procedures of Examples I, II and III are repeated exceptthat 8,10-dimethyl-8-vinyl-lO-octadecene-1,18-dioic acid replaces theeicosene-dioate. The corresponding mono-, diand tri-adducts of the acidare obtained.

EXAMPLE VIII The procedure of Example IV is repeated except thathexadecadiene-6,10-dioic acid replaces the eicosadiene dioic acid toform the corresponding mono-, diand triadducts.

EXAMPLE IX The procedure of Example VIII is repeated except that thecorresponding methyl-ester replaces the acid to produce the esteradducts.

The above examples illustrate that this invention is not limited to theparticular embodiments shown as the adducts readily form with the acids,esters, ketones and amides having from 16 to 28 carbon atoms aspreviously described. Furthermore, this invention is not limited, in thecase of diesters, to methyl esters. If desired, other diesters may beprepared from the methyl esters by ester interchange, or alcoholysis, i.e., the reaction of the methyl ester with an alcohol in the presence ofsuitable catalysts. The use of other esters generally is not pre ferredfor the curing agents that are described below since there is noadvantage resulting from such a substitution of esters, but rather ithas the eflfect of increasing the cost without a proportionalimprovement in the product. Thus, such lower ester-adducts as the ethyl,propyl and butyl adducts are included within the scope of thisinvention, although not limited thereto as it is well known that theprocess of ester interchange is not limited to lower alcohols but mayalso extend to higher alcohols as myristyl alcohol, stearic alcohol, andthe like and also to aromatic alcohols.

The polyfunctional adducts of this invention can be further reacted withother polyfunctional compounds, as polyhydric alcohols, to form highermolecular weight adducts.

Generally, the adduct is formed in solutions of organic solvents whichare immiscible with Water such as chloroform, benzene, carbontetrachloride, and the like. Such a reaction medium is designed topermit the removal of excess anhydride by washing with water. When allthe excess anhydride is removed, as indicated by simple titration, thesolvent is stripped to produce the final product. With adequate washing,recrystallization is generally not required. In order to obtain maximumyields of relatively pure products it is preferred that the anhydride bepresent in slight excesses of the mole ratio required to produce themono, di-, or tri-adducts of the acids, esters, ketones or amides, asthe case may be. The specific quantities required will vary in eachinstance depending on the particular product desired but in all casesthe use of slight excesses over the calculated amount needed to producethe mono-, di-, or tri-adduct in quantitative yield is preferred. Whenthe quantity is substantially between that required to produce themonoand the di-adduct on the one hand and the diand tri-adduct on theother hand, mixturesof the two are obtained. As previously indicated,separation of the mixture is often unnecessary as it may be used for thepurposes hereinafter indicated without any adverse ctfect. In general,mole ratios will range from about 1:1 to about 3:1 of the anhydride tothe acid, ester, ketone or amide, there being no preferred range as thiswill depend on the desired final product.

It has been found that more than 3 moles of the anhydride apparentlydoes not add easily to the acid, ester, ketone or amide under the usualconditions of temperature and pressure.

The temperature range under which the adducts are preferably formed isabout ISO-200 C., although lower temperatures may be used, c. g., in theorder of C. At lower temperatures considerably greater time is requiredto complete the reaction whereas higher temperatures, e. g., in theorder of 250 C., cause: degradation. In order to operate at preferredtemperatures and yet reduce oxidation losses to a minimum it isdesirable that the reaction be conducted in an atmosphere of an inertgas such as carbon dioxide or nitrogen.

As previously indicated the products of this invention are of unusualvalue as improved curing agents for polyglycidyl ethers. Not only dothey increase the hardness and flexibility of such resins withoutrequiring an increase in curing time but the diand tri-adducts impartimproved resistance to solubility. Such resins containing the adducts ofthis invention are further characterized as being highly resistant tothe adsorption of water, thus making them highly useful in manyapplications where water resistance is of importance. Because castresins prepared with these new adducts are extremely hard they may beused for, among other things, stamping sheet metal and in the repairs ofautomobile bodies. Their resistance to breakage, shattering and solventsmakes them highly useful in the packaging, storing and shipping of allkinds of liquids particularly chemicals.

Table I shows typical tests on the adducts of the dimethyl esters of8,12-eicosadiene 1,20-dioate.

Table 1 [Film sample: EPON 1001. Cure cycle: 30 min. at 150 0.]

Min. at Room Temper- Amount ature Adduct 1001 Condition Knife Test 15Min. Boll- Color (PHR) When Hot mg Water Toluene Methyl Isobntyl KetoneFlexible Softened- Softened Unaffected" Dark Amber.

do do dn do Do. Do. Do. Do. D0.

D0. Do. Do.

1 Epoxy resin-product of Shell Chemical Corporation.

When similar tests are performed on acid adducts comparable results areobtained and in some instances they are better as they tend to be harderwhen hot and do not soften as readily in toluene and methylisobutylketone. In general, it will be found that the acid andester-adduct are most preferred while the ketone and amide-adducts arethe least preferred.

Table II shows typical tests on the same adducts used in cast resins.

satisfactory as will be exhibited by less satisfactory solubilitycharacteristics, water swelling, brittleness, softness and the like.

The resins may be cured by conventional methods, e. g., by baking or bythe application of heated forced air. Generally, it is adequate to curethe film compositions at 150 C. for about minutes whereas the castcompositions will require about 125 C. for about 4 hours. It ispreferred that these resins be cured at temperatures Table 11 [Castingsample: EPON 828. Cure cycle: 4 hours at 125 0.]

Bareol Hardness 3 Hr. Boiling 3 Hr. Boiling Acetone Water Amount Adduct828 Color (PHR) Percent Percent W.

R. T. 60 80 100 120 Bareol W. Barcol Change Change 249 0 Rubbery Like) 0+1. 0 Disintegratei Dark Amber.

118 28 0 (Foamed) 0 3. 55 0 d0 D0.

1 Epoxy resin-product of Shell Chemical Corporation.

Results comparable to the film composition are ootained in the case ofacid, ketoneand amide-adducts, but as in that case, the acid-adductsare, in certain instances, preferred over the ester-, ketoneandamideadducts. Such factors as the specific application to which theresin is to be put, its cost, relative ease of handling, and similarconsiderations will often determine whether the ester-, acid-, ketoneoramide-adduct is preferred.

In preparing polyglycidyl resins cured with the novel productsof thisinvention, the optimum amount of the adduct is, in most cases, justsuflicient to supply one anhydride ring for each glycidyl group. Theexact optimum amount will vary depending on the particular resins andthe particular mono-, dior tri-adduct being used. In theory, eachglycidyl group of the resin reacts with the anhydride group to produceester groups almost exclusively without the formation of water. As theglycidyl group and the anhydride are difunctional, a highly cross-linkednetwork results with the ester groups serving to connect these networks.Thus, in order to provide the stoichiometric quantity of curing agenthaving the required number of anhydride groups for each glycidyl group,it may be necessary at times to provide considerable quantities of thecuring agent to the extent that the amount of the curing agent presentmay exceed the amount to the resin on a weight basis. In any case, thecuring agent will always be present in such sizeable quantities that itis a major ingredient. Therefore, if too much or too little curing agentis present the final product will have excesses of anhydride or glycidylgroups, respectively, resulting in something less than optimum curings.The final product will then be considerably less wherein R is a divalentacyclic carbon chain having from 14 to 26 carbon atoms, said-divalentchain having two ethylenic linkages which are at least four carbon atomsremoved from the carbonyl groupsand R is a functional group selectedfrom the group consisting of lower alkyl, OH, NH and CR andrnixturesthereof, R being lower alkyl, said product b ei n g prepared in theliquid phase in the presence of an inert solvent at temperatures rangingfrom 100 C...to about 250 C., the anhydride being present in a ratio ofabout l to about 3 moles per mole of the carbonyl compound.

2. The product of claim 1 in which R is OH.

3. The product of claiml in which R is OH and 9 10 5. The product ofclaim 1 in which R, is --OR References Cited in the file of this pat'enf6. The product of claim 1 in which R is --OCH and UNITED STATES PATENTSR is (CH9FCH=3HCH*CH2CH:H(CH2)P' 2188 882 Clocker Jan 30 1940 R Theproduct of 613.1111 1 1n WhlCh R is 0CH and 5 0: Sutherland May 19482,496,358 Ross Feb. 7, 1950 2,582,235 Cowan Jan. 15, 1952 H 2,671,810Coflman Mar. 9, 1954 35 2,745,844 Dazzi May 15, 1956 s. The product ofclaim 1 in which R is -5111, 10 OTHER FEFERENCES 9. The product of claim1 in which R is NH and Flatt! Maleic Anhydflde Derivatives (1 Pages

1. THE REACTION PRODUCT OF MALEIC ANYDRIDE WITH A COMPOUND HAVING THEFORMULA